CN101314732B - Continuous aromatization modification method for hydrocarbons - Google Patents
Continuous aromatization modification method for hydrocarbons Download PDFInfo
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- CN101314732B CN101314732B CN2007100998573A CN200710099857A CN101314732B CN 101314732 B CN101314732 B CN 101314732B CN 2007100998573 A CN2007100998573 A CN 2007100998573A CN 200710099857 A CN200710099857 A CN 200710099857A CN 101314732 B CN101314732 B CN 101314732B
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Abstract
A continuous hydrocarbon aromatization and modification method comprises the following steps: (1) heating hydrocarbon materials, and feeding into a moving bed reactor from the top to contact and react with an aromatization catalyst, (2) lifting the spent catalyst from the bottom of the moving bed reactor by a spent catalyst elevator through a riser line to a spent catalyst separation hopper, separating with the lifting gas, feeding into a catalyst regenerator from the top through a pressure transformation and flow control region, passing through the buffer zone, the burning region, the drying zone and the cooling zone in the catalyst regenerator sequentially from top to bottom, and introducing oxygen-containing regeneration gas into the burning zone to burn and regenerate the spent catalyst, and (3) lifting the regenerated catalyst flowing from the bottom of the catalyst regenerator and adding into the moving bed reactor from the top. The method is suitable for aromatization reaction of naphtha with low octane number, and has the advantages of sufficient regeneration and burning of catalyst, less specific area loss of catalyst, long service life of the regenerated catalyst and low energy consumption of the regeneration operation.
Description
Technical field
The present invention is a continuous aromatization modification method for hydrocarbons, specifically, be a kind of be raw material with the low octane rating petroleum naphtha, in moving-burden bed reactor-continuous regeneration set, produce aromatic hydrocarbons or the high octane gasoline component of low olefin-content and the method for liquefied gas.
Background technology
Along with the appearance of unleaded gasoline and new gasoline standard, part low octane value gasoline, light naphthars such as the tops of for example reforming, condensate oil, partial hydrogenation coker gasoline and straight-run spirit are badly in need of seeking suitable processing technology.Though this part petroleum naphtha is fit to do ethylene raw, because its vapour pressure is higher, transportation is difficulty relatively, if there is not ethylene unit near the enterprise, is difficult to ethylene raw.At present, oil refining enterprise is produced the main device or the catalytic reforming of aromatic hydrocarbons and high-octane rating clean gasoline blend component, but catalytic reforming is used the platiniferous noble metal catalyst, and raw material impurity is required harshness, invests huge.Late 1970s, owing to the discovery of ZSM-5 shape-selective molecular sieve, can not use under the condition of noble metal catalyst at non-hydrogen, petroleum naphtha and carbon number is less, be mainly C
5The following hydrocarbon conversion is an aromatic hydrocarbons, while by-product hydrogen and high-quality liquefied gas, and its main products BTX aromatics is an important chemical material, also can mix with gasoline and convert, concoct, and improves gasoline octane rating.This technology is called aromatization technology.This has opened up an effective way for the utilization of refinery's low octane rating petroleum naphtha.
CN1032697C discloses a kind of catalytic modification of poor quality gasoline-aromatization method, this method contacts inferior patrol with catalyzer carries out the echelon reaction, be about to raw material and feed first fixed-bed reactor earlier, at 300～550 ℃, 0.05～1.2MPa, weight space velocity 0.2～1.0h
-1Conditions of non-hydrogen under react, resultant is through gas-liquid separation, C
5Above liquid obtains gasoline fraction by fractionation, in the reaction product less than C
4Gas send into second reactor through preheating, at 480～650 ℃, 0.05～1.5MPa, volume space velocity 20～2000h
-1Condition under carry out aromatization, the aromizing product obtains being rich in the gas and the aromatic hydrocarbons mixture of hydrogen after gas-liquid separation.Used aromatized catalyst is made up of the HZSM-5 molecular sieve and the binding agent of modification, described molecular sieve modified component is two or three in Zn, Al or the rare earth metal, and binding agent is selected from a kind of or aluminum oxide in aluminum oxide, silicon oxide or the clay and the mixture of silicon oxide.Described reactor be two in parallel can switch, the regenerated fixed bed, in about two weeks in catalyzer one way life-span, decaying catalyst is by feeding oxygen-containing gas, at 550～700 ℃ of coke burning regenerations in fixed bed.
CN1261535C discloses the method that a kind of straight-run spirit upgrading prepares gasoline with low olefine content, this method is mixed straight-run spirit with the C 4 olefin cut, under 0.2～0.6MPa, 300～500 ℃ condition, in fixed-bed reactor with contain the catalyzer contact reacts of HZSM-5, the dry gas in the separated product, liquefied gas and gasoline component then.Also can contain the modified component that is selected from antimony or mixed rare-earth oxide in the described catalyzer.
CN1212376C discloses a kind of lighter hydrocarbons non-hydrogen modifying catalyst and preparation method and application art.Described catalyzer is made up of the carrier of the mixed rare-earth oxide that contains 0.1～5.0 quality % or weisspiessglanz, 95.0～99.1 quality %, and wherein carrier is made up of the HZSM-5 zeolite of 50～80 quality % and the gama-alumina of 20～50 quality %.Described lighter hydrocarbons non-hydrogen upgrading carries out in fixed-bed reactor, and reaction product is separated liquid the stop bracket gasoline that obtains dry gas, high-quality liquefied gas and low olefin-content again through gas-liquid separation.Decaying catalyst is done resurgent gases with oxygen containing stack gas or nitrogen and is burnt carbon, and the resurgent gases oxygen level is 0.3～2.1%, and regeneration temperature is that 350～450 ℃, regeneration pressure are normal pressure～0.3MPa.
CN1651141A discloses a kind of aromatized catalyst and preparation thereof and has used, and adopting Zn, phosphorus and rare-earth element modified HZSM-5 molecular sieve and REY molecular sieve is the catalyst activity component.With the lower inferior patrol of octane value is raw material, carries out the moving-bed aromatization under the non-hydrogen state, and temperature of reaction is 350～550 ℃, and pressure is 0.1～0.5MPa, and air speed is 0.5～5h
-1Catalyst regeneration temperature is 400～550 ℃, and the residence time in revivifier is 1～600 minute, adopts air regenesis.
CN1485414A discloses the method for a kind of catalytically cracked gasoline non-hydrogen aromatization and desulfurization, this method is introduced the reactor that molecular sieve catalyst is housed with the full cut of catalytically cracked gasoline, carry out alkene aromizing and hydrodesulfurization reaction, again reacted product is carried out alkali-free sweetening, obtain gasoline products, its temperature of reaction is that 100～550 ℃, pressure are that 0.01～5.0MPa, air speed are 0.1～20h
-1The used aromatized catalyst active ingredient of this method is one or more in ZSM-5, ZSM-11, ZSM-12, ZSM-35, MCM-22, Y molecular sieve and the beta molecular sieve, and the modified component of molecular sieve is one or more of rare earth element, VIB, VIII family element, haloid element, Mg, Zn, P and Na.Aromatization can carry out in moving-bed, fluidized-bed or fixed bed, but does not provide concrete catalyst regeneration process.
USP4795845 discloses a kind of aliphatic hydrocarbon aromatization method that is the catalyst activity component with phosphorous and ZSM-5 molecular sieve gallium, and this method contacts the catalyzer of inactivation with oxygen containing resurgent gases, regenerate by burning.Regeneration can be carried out in fixed bed or moving-bed, and resurgent gases is capable of circulation.This patent points out that also the regeneration of decaying catalyst can be divided into for two steps, the first step uses the lower gas of oxygen level to burn, the burning process oxygen content gas is 1.0mol%, then oxygen content gas slowly is increased to 7.0mol% and burns again, basic identical until the out temperature of catalyst bed.
USP4724271 discloses a kind of continuous regeneration method of aromatized catalyst, and this method uses the ZSM-5 molecular sieve of Ga modification to be catalyzer.The scorch region of decaying catalyst by revivifier contained oxygen cycle gas with exsiccant contact, reclaim flue gas and air mixed from scorch region, the moisture of removing wherein through super-dry enters scorch region again, thereby forms the circulation of scorch region gas.Catalyzer after burning enters drying zone, utilizes dry air to carry out drying.Described scorch region is radially moving bed, and drying zone is an axial moving bed.
USP6395664B1 discloses the continuous regeneration method of the ZSM-5 aromatized catalyst of a kind of Ga of comprising and P, catalyzer exposes inactivation in hydrogen to the open air under the high temperature more than 500 ℃, only burn and can not recover activity of such catalysts, the need use contains weakly acidic ammonium salt or aqueous acid is handled the catalyzer after burning.The regeneration of decaying catalyst divides four-stage: burn, cool off, handle and dry with ammonium salt-containing or faintly acid water vapor air-flow, wherein scorch region adopts resurgent gases round-robin mode to carry out moving-bed to burn for one section.
USP4304657 discloses a kind of improved naphtha aromtization process, is catalyzer with the HZSM-5 of zinc modification, at 345～815 ℃, under the condition of 0.1～3.5MPa, with CO
2Or nitrogen dilutes petroleum naphtha and CO during dilution to petroleum naphtha
2Or the mol ratio of nitrogen is 1:1～20.This method can improve the H in the naphtha aromtization gaseous product
2/ CH
4Mol ratio, and reduce C in the product liquid
10The content of above aromatic hydrocarbons.
USP6245219B1 discloses a kind of naphtha reforming method, the catalyzer that this method is used is carrier with mesopore acidic silicic acid salt, at least a oxide compound or the sulfide that is selected from Zn, Ga, In, Fe, Sn and B of load, and by carrying out modification with alkaline earth metal hydroxides or silicoorganic compound impregnated carrier, the preferred ZSM-5 of described silicate.Use the petroleum naphtha that contains 25% alkane and naphthenic hydrocarbon at least to be raw material, at 200～538 ℃, 70～2100KPa, weight space velocity 0.5～25h
-1, hydrogen/hydrocarbon mol ratio 0～10 is preferably under 4 the condition and carries out naphtha reforming, C in the products therefrom
1～C
4Gas yield significantly be reduced to below the 20 weight % and the C of product liquid
8Be rich in p-Xylol in the component.
Summary of the invention
The method that the purpose of this invention is to provide a kind of low octane rating petroleum naphtha continuous aromatization modification, this method can reduce dry gas yied when improving gasoline octane rating or producing aromatic hydrocarbons, and produces the high-quality liquefied gas of low olefin-content.
Continuous aromatization modification method for hydrocarbons of the present invention comprises the steps:
(1) hydrocarbon raw material heating back is sent into from the top in the moving-burden bed reactor to contact with aromatized catalyst and reacted, reaction product obtains gasoline component and liquefied gas through fractionation,
(2) reclaimable catalyst that will come out from the moving-burden bed reactor bottom, being promoted to reclaimable catalyst separation hopper by the reclaimable catalyst lifter through lift line separates with lifting gas, then through excess pressure conversion and flow control district, enter catalyst regenerator from the top, pass through buffer zone, scorch region, drying zone and cooling zone in the catalyst regenerator from top to bottom successively, in scorch region, feed the coke burning regeneration that oxygen containing resurgent gases is carried out reclaimable catalyst
(3) from the effusive regenerated catalyst in catalyst regenerator bottom, separate hopper through regenerated catalyst lifter, regenerated catalyst lift line, regenerated catalyst and enter moving-burden bed reactor.
The present invention adopts moving-burden bed reactor to carry out the aromatization modification reaction of low octane rating petroleum naphtha, is reflected under the non-hydrogen atmosphere and carries out.Catalyst regenerator is divided into buffer zone, scorch region, drying zone and cooling zone from top to bottom, makes the catalyst regeneration operation be easier to control, and the regeneration energy consumption reduces, and catalyst regeneration is effective, long service life.The inventive method can implement device long-term operation, the product reasonably optimizing more that distributes.
Description of drawings
Fig. 1 stacks up and down for the present invention adopts two reactors, and the revivifier scorch region adopts the process flow diagram of two-section radial bed.
Fig. 2 stacks up and down for the present invention adopts two reactors, and two sections scorch regions of revivifier adopt the process flow diagram of footpath, axial bed.
Fig. 3 adopts four tandem reactors that stack in twos for the present invention, and the revivifier scorch region adopts the process flow diagram of two-section radial bed.
Fig. 4 adopts four tandem reactors that stack in twos for the present invention, and two sections scorch regions of revivifier adopt the process flow diagram of footpath, axial bed.
Fig. 5 is the fractionating system schematic flow sheet of the inventive method aromatization reaction products.
Embodiment
The inventive method adopts moving-burden bed reactor and revivifier to carry out the aromizing of low octane rating petroleum naphtha, and catalyst regenerator is divided into buffer zone, scorch region, four districts of drying zone and cooling zone from top to bottom, pressure conversion and flow control district are arranged on revivifier top, can realize burning under elevated pressures and carry out, the buffer zone of cooperation revivifier can be realized the continuous flow of catalyzer, in addition, buffer zone also has the effect of preheating catalyst.Reclaimable catalyst is preheating in buffer zone, in scorch region, burn carbon deposit in the catalyzer to recover its activity, in drying zone, remove moisture, in the cooling zone, cool, to reduce the requirement of follow-up pipeline and equipment to material, simultaneously, the cooling zone also can make the gas preheating that part enters drying zone.Thereby the operation energy consumption of revivifier can be reduced in the buffer zone that is provided with in the revivifier and cooling zone.
The described scorch region of the inventive method comprises at least two sections scorch regions of arranged vertical from top to bottom, preferably is made up of two sections scorch regions of arranged vertical from top to bottom.Adopt two sections empyreumatic methods that reclaimable catalyst is burnt, but the gasinlet temperature and the oxygen level of each section of independent control scorch region, the turndown ratio of expansion revivifier.Two sections burn the temperature that also can make each scorch region and more are tending towards relaxing, the oxygen level that enters one section scorch region gas can tune to proper range, the oxygen level that enters two sections scorch region gases can suitably improve than one section so that one section scorch region unreacted completely catalyst carbon deposition further react completely at two sections scorch regions.Burn to be reflected at comparatively and carry out under the demulcent condition, can reduce local hot spots, specific surface area fall in each burning process of catalyzer is reduced, prolong the work-ing life of catalyzer.
Described two sections scorch regions can be selected different structures for use, and first scorch region that preferably comes top is a radial bed, and second scorch region that comes the bottom is axial bed, and perhaps two sections scorch regions are radial bed.
The inventive method will be passed through desulfurization and drying from the flue gas that scorch region is discharged, becoming resurgent gases with the gas mixture of air or air and nitrogen after mixed is used to burn, form the circulation of scorch region gas, to reduce environmental pollution and to reduce the influence of moisture to catalyst activity.Described resurgent gases is divided into two strands, respectively through entering one section scorch region and two sections scorch regions after the heating.The optimal way that resurgent gases enters scorch region is: one in two bursts of resurgent gaseses enters the reclaimable catalyst bed from the top of one section scorch region in entad mode, and another strand enters the reclaimable catalyst bed from the bottom of two sections scorch regions in the centrifugal mode; Another kind of mode is that described two bursts of resurgent gaseses enter one section scorch region and two sections scorch regions respectively from the middle part.The flue gas of two sections scorch region generations can be discharged from the top or the bottom of one section scorch region.
In the inventive method, can control the oxygen level and the resurgent gases temperature in of the resurgent gases that enters scorch region, enter preferred 0.1～3.0 volume % of oxygen level of the resurgent gases of one section scorch region, enter preferred 0.2～5.0 volume % of oxygen level of the resurgent gases of two sections scorch regions, more preferably 0.3～2.0 volume %.The temperature in that enters the resurgent gases of one section scorch region is 350～600 ℃, preferred 400～500 ℃; The temperature in that enters the resurgent gases of two sections scorch regions is 400～600 ℃, preferred 440～550 ℃.The revivifier control pressure is the preferred 0.2～1.0MPa of 0.1～2.0MPa.Reclaimable catalyst is 10～600 minutes in the residence time of scorch region, preferred 60～480 minutes.
The bottom of the described catalyst regenerator of the inventive method is the cooling zone, and top, cooling zone is drying zone.Earlier cold gas is fed the cooling zone of catalyst regenerator during operation, mixed with another part dry gas again by the gas that comes out in the cooling zone, after heating, enter drying zone.Described cold gas and dry gas are selected from the miscellany of nitrogen, air or nitrogen and air.Oxygen level in cold gas and the dry gas is not more than 21 volume %.
The temperature of described drying zone inlet gas is 120～600 ℃, and preferred 250～500 ℃, the temperature of cooling zone exit gas is not more than 200 ℃.
Described drying zone expellant gas can be discharged system or be introduced the scorch region recycle, the flue gas that is about to after drying zone expellant gas and the desulfurization is mixed, and the drying device removes wherein moisture and mixes the formation resurgent gases with the gas mixture of air or air and nitrogen again and enter scorch region.
Moving-burden bed reactor of the present invention comprises at least two, and the reactor of preferred two to four polyphones is equipped with process furnace before each reactor, and the reaction raw materials that enters each reactor all needs to heat by process furnace.Reaction raw materials enters first reactor after heating, the reaction product of discharging from this reactor enters next reactor again after heating, and the rest may be inferred.The arrangement mode of described a plurality of reactors can be and stacks up and down or place side by side, and when adopting four reactors, two reactors can be stacked up and down becomes one group, two bank of reactor is placed side by side again, and catalyst devator is set between every group.
The described catalyst devator of the inventive method uses circulating nitrogen gas the catalyzer of reactor bottom to be promoted to the top of revivifier top or follow-up reactor, all be provided with revivifier top stream exit at reactor and separate cleaning apparatus, be about to the separation hopper that catalyzer or reclaimable catalyst are promoted to reactor or revivifier top, in separating hopper with catalyzer or reclaimable catalyst and nitrogen separation, the nitrogen that carries the part catalyst dust enters dust collection, behind the dust-filtering in the air-flow, part nitrogen returns the separation hopper behind the elutriation blower fan, another part promotes the gas recycle as catalyzer.
Hydrocarbon raw material of the present invention is that initial boiling point is 30～80 ℃, and final boiling point is 130～200 ℃ a hydrocarbon fraction, the naphtha fraction that preferred virgin naphtha, reformation tops, condensate oil or hydrogenation coking process produce.
The catalytic temperature of hydrocarbon raw material of the present invention and catalyzer is 250～600 ℃, and preferred 280～500 ℃, pressure is 0.1～2.0MPa, preferred 0.2～1.0MPa, more preferably 0.3～0.8MPa.The suitable charging mass space velocity of reaction is 0.1～5.0h
-1, preferred 0.2～1.0h
-1Be reflected under the conditions of non-hydrogen and carry out, raw material need not to give refining, directly uses to get final product.
The catalyzer that the inventive method is used does not contain precious metal, and use high silicon five-element circular type zeolite or contain zinc or the high silicon pentasil zeolites of gallium, rare earth element and VA family element is active ingredient, described zeolite is h-type zeolite, and binding agent is selected from silicon-dioxide or aluminum oxide, preferred aluminum oxide.The preferred ZSM-5 of described high silicon five-element circular type zeolite, ZSM-11 or ZSM-12, the mol ratio of its silica is preferred 10～200, and more preferably 20～100; The preferred phosphorus of VA family element, antimony or bismuth; The preferred mixed rare earth oxide of rare earth element wherein contains lanthanum trioxide 20～40 quality %, cerium oxide 40～60 quality %, Praseodymium trioxide 10～18 quality %, Neodymium trioxide 2～10 quality %.The preferred catalyzer of the inventive method comprises the rare earth oxide of ZnO, 0.1～3.0 quality % of 0.5～3.0 quality %, the VA family element of 1.0～5.0 quality %, all the other are complex carrier, and described complex carrier comprises the high silicon five-element circular type zeolite of 30～50 quality % and the binding agent of 50～70 quality %.
Below in conjunction with description of drawings the present invention, but the present invention is not limited to this.
The flow process of reaction raw materials is among Fig. 1: light naphthar enters interchanger 102 through pipeline 101, after the reaction product heat exchange, enter process furnace 104 heating after pipeline 105 enters first reactor 106 through pipeline 103, contact back generation aromatization with catalyzer wherein, reacting rear material enters process furnace 108 through pipeline 107 and heats once more, enter second reactor 110 through pipeline 109 then, contact the continuation reaction with catalyzer wherein, reacting rear material is through pipeline 111, after entering interchanger 102 and reaction raw materials heat exchange, go fractionating system through pipeline 301.The catalyst bed of described first and second reactor is radial bed (not marking among the figure).
The flow process of catalyzer is: from the effusive decaying catalyst in reactor 110 bottoms is reclaimable catalyst, enter reclaimable catalyst lifter 113 through catalyzer tremie pipe 112, be promoted to reclaimable catalyst with circulating nitrogen gas by pipeline 114 and separate hopper 201, catalyzer and lifting stream of nitrogen gas are separately in separating hopper 201, the stream of nitrogen gas of carrying the part dust enters dust collecting system through pipeline 200, dust is wherein removed the back recycling, do not mark among the figure.Enter pressure conversion and flow control hopper 203 by separating hopper 201 isolated reclaimable catalysts by pipeline 202, enter catalyst regenerator 205 through pipeline 204 again, control revivifier pressure is 0.1～2.0MPa, preferred 0.2～1.0MPa, more preferably 0.5～1.0MPa.In catalyst regenerator 205, one section scorch region 208 (radial bed) that reclaimable catalyst passes through buffer zone 206 (axially bed), catalyzer tremie pipe 207 from top to bottom successively, surrounded by screen cloth, catalyzer tremie pipe 209, the two sections scorch regions 210 (radial bed), catalyzer tremie pipe 211, drying zone 212 (axially bed), catalyzer tremie pipe 213, cooling zone 214 (the axially bed) that surround by screen cloth.Reclaimable catalyst is 10～600 minutes in the residence time of whole scorch region, preferred 60～480 minutes.The regenerated catalyst that comes out from revivifier 205 bottoms, enter regenerated catalyst lifter 218 through pipeline 215, bottom hopper 216, pipeline 217 successively, with circulating nitrogen gas regenerated catalyst is separated hopper 220 by the regenerated catalyst that pipeline 219 is promoted to reactor 106 tops, regenerated catalyst and stream of nitrogen gas are separated, the stream of nitrogen gas of carrying the part dust enters dust collecting system through pipeline 221, and dust is wherein removed the back recycling.Separate hopper 220 isolated regenerated catalysts by regenerated catalyst and enter reactor 106, in reactor 106, rely on self gravitation to enter second reactor 110, enter reclaimable catalyst lifter 113 again, regenerate again by catalyzer tremie pipe 222.
In above-mentioned catalyst reaction-reprocessing cycle, promoting the used nitrogen of catalyzer can be replenished by reclaimable catalyst lifter 113, regenerated catalyst lifter 218 and bottom hopper 216 places.
Gas circulating in the catalyst regenerator is: the flue gas that scorch region produces comes out from the bottom of one section scorch region 208, enters the digester 224 that fume desulfurizing agent is housed through pipeline 223 and removes wherein SO
2, fume desulfurizing agent can adopt calcium-based desulfurizing agent or other high-temperature flue gas sweetening agent.Remove SO
2After flue gas through pipeline 225, small part is by pipeline 226 discharge systems, major part enters interchanger 227, after resurgent gases heat exchange after the cooled dehydrated, enter air cooler 229 through pipeline 228, enter moisture eliminator 231 through pipeline 230 again, the water-content in the flue gas is reduced to below the 2000ppm, preferably reduce to below the 1000ppm, more preferably reduce to below the 200ppm.Flue gas after the dehydration through pipeline 232 with from the freezing air of pipeline 233 or air with form resurgent gases after the mixed gas of nitrogen mixes.Resurgent gases through pipeline 234 to regeneration blower fan 235, after pipeline 236 enters interchanger 227 and the hot flue gas heat exchange from scorch region, a part enters well heater 238 through pipeline 237 and is heated to 350～600 ℃, be preferably 400～500 ℃, through pipeline 239 from entering the top of one section scorch region (radial bed) 208, controlling one section resurgent gases inlet oxygen level is 0.1～3.0 volume %, preferred 0.3～2.0 volume %, resurgent gases radially enters reclaimable catalyst bed with the annular space 255 of regeneration wall with radial inflow by radial bed and contacts with it.The flue gas that burns the back generation enters space 253, discharges from one section scorch region bottom again, circulates through pipeline 223.Another part resurgent gases after interchanger 227 heat exchange is through pipeline 240, after mixed from the mixed air of the air of pipeline 256 or nitrogen and air, enter well heater 242 through pipeline 241 and be heated to 400～600 ℃, preferred 440～550 ℃, controlling its oxygen level is 0.2～5.0 volume %, preferred 0.3～3.0 volume %, enter space 254 through pipeline 243, enter the radial bed 210 of second section reclaimable catalyst with centrifugal radial, and contact with reclaimable catalyst, the flue gas that burns generation enters pipeline 223 by one section scorch region bottom and circulates.
From the nitrogen of pipeline 244 with mixed from the air of pipeline 245 after, enter the middle part in catalyst regenerator internal cooling district 214 through pipeline 246, from cooling zone 214 top expellant gas after pipeline 248 and mixed gas from the nitrogen of pipeline 247 or nitrogen and air mix, enter well heater 250 through pipeline 249 and be heated to 120～600 ℃, preferred 250～500 ℃, enter catalyzer drying zone 212 through pipeline 251.The 252 discharge systems from drying zone 212 expellant gas from pipeline, or enter interchanger 227 through pipeline 257 and circulate.
Fig. 2 and Fig. 1 flow process are basic identical, and one section scorch region 208 of different is catalyst regenerator is radial bed, and two sections scorch regions 211 be axially bed.Connect by catalyzer tremie pipe 209 between two sections scorch regions of Fig. 2.Enter beds from the resurgent gases of pipeline 239 from the middle part of one section scorch region, contact with spent agent.Another burst resurgent gases enters two sections scorch regions 211 through pipeline 243 from the middle part, the gas that burns generation is through grid distributor 254 ' the enter space 253 that one section scorch region surrounds, after the flue gas of one section scorch region generation mixes, circulate through pipeline 223 by one section scorch region top.The excess air of drying zone 212 is directly discharged through pipeline 252.
Fig. 3 and Fig. 1 flow process are basic identical, and different is that reactive moieties is made up of the reactor of four polyphones.From the light naphthar of pipeline 101 through interchanger 102 and reaction product heat exchange, enter process furnace 104 heating through pipeline 103, entering first reactor 106 through pipeline 105 radially contacts with catalyzer and carries out aromatization, reacting rear material enters through pipeline 107 and enters the 110 continuation reactions of second reactor after process furnace 108 heats once more, the material of being discharged by reactor bottom enters process furnace 112 through pipeline 111 and heats once more, enter the 3rd reactor 114 through pipeline 113 then, radially contact the continuation reaction with catalyzer, reacting rear material enters process furnace 116 through pipeline 115 and heats once more, enter the 4th reactor 118 through pipeline 117, radially contact the continuation aromatization with catalyzer.Reacted material goes interchanger 102 and reaction raw materials heat exchange through pipeline 119, enters the product fractionating system through pipeline 301.
The catalyzer of discharging from second reactor, 110 bottoms enters catalyst devator 121 through catalyzer tremie pipe 120, utilize circulating nitrogen gas catalyzer to be promoted to the catalyst separating hopper 123 at the 3rd reactor 114 tops through pipeline 122, catalyzer and lifting stream of nitrogen gas are separated stream of nitrogen gas recycle after pipeline 123 removes dust collecting system of carrying dust.The catalyzer of separating is after catalyzer tremie pipe 124 relies on self gravitation through the 3rd reactor 114 and the 4th reactor 118, enter reclaimable catalyst lifter 127 through catalyzer tremie pipe 126, utilize nitrogen the reclaimable catalyst that reclaimable catalyst is promoted to the catalyst regenerator top to be separated hopper 201 through pipeline 128, enter pressure conversion and flow control hopper 203 with catalyzer and after promoting nitrogen separation, pass through the buffer zone at catalyst regenerator top then, enter the regeneration that scorch region carries out decaying catalyst.
The reactive moieties of Fig. 4 flow process is identical with Fig. 3, and regeneration section is identical with Fig. 2.
Fig. 5 is the fractionation schematic flow sheet of the inventive method aromatization reaction products.From the product of reactive system through pipeline 301, after entering water cooler 302 coolings, enter flash tank 304 through pipeline 303 and be separated into gas-liquid two-phase, after the pipeline 305 of rich gas by flash tank 304 tops enters rich gas compressor 306 compressions, enter the middle part that absorbs desorption tower 308 by pipeline 307, dry gas is from absorbing desorption tower 308 cats head through pipeline 312 discharge systems.Material at the bottom of absorption Analytic Tower 308 towers enters the middle part of stabilizer tower 315 by pipeline 313, in stabilizer tower 315, liquefied gas is separated with high octane gasoline component, liquefied gas by cat head through pipeline 316 discharge systems, gasoline component is discharged from tower bottom tube line 314, a part is by pipeline 317, after liquid phase material that flash tank bottom line 309 is discharged mixes, send the top of absorption desorption tower 308 with raw gasline pump 310 back to through pipeline 311, rest part as gasoline product by pipeline 318 discharge systems.Described dry gas is hydrogen, methane, ethane and ethene.
Further specify the present invention below by example.
Example 1
The used catalyzer of preparation the present invention.
(1) preparation complex carrier
Get 67.6 kilograms of pseudo-boehmite powder (Sasol company produces,
Alumina content 74 quality %), stirring and joining 300 kilograms of concentration down is in the aqueous nitric acid of 1.1 quality %, stir 2 hours peptizations after, add 55.0 kilograms of silica and be 60 HZSM-5 zeolite powder (zeolite content 91%), high-speed stirring 3 hours.The slurries of making are splashed in the oil ammonia column that 8 quality % ammoniacal liquor are housed, the wet bulb that forms in the oil ammonia column is taken out, 60 ℃ of dryings 10 hours, 550 ℃ of roastings 3 hours obtain complex carrier, for containing the alumina globule of HZSM-5 zeolite 50 quality %.
(2) preparation catalyzer
Get 50 kilograms of complex carriers, with 50 kilograms contain zinc nitrate 4.7 quality %, (wherein lanthanum trioxide accounts for 31% to chlorination mishmetal 3.0 quality %, cerium oxide 51%, Praseodymium trioxide 14%, Neodymium trioxide 4%), the mixing solutions of phosphoric acid 6.6 quality % dipping is 30 minutes, 110 ℃ of dryings 24 hours, 550 ℃ of roastings 5 hours are handled in 550 ℃ with water vapor then and were obtained catalyst A in 4 hours.
Catalyst A contains zinc oxide 2.0 quality %, phosphorus 2.0 quality %, mixed rare-earth oxide 1.0 quality %, and all the other are complex carrier.The specific surface area of catalyst A is 303m
2/ g.
Example 2
By technical process shown in Figure 1, use catalyst A, be raw material with the virgin naphtha shown in the table 1, under conditions of non-hydrogen, carry out the aromatization test, the temperature in of controlling each reactor is 400 ℃, reaction pressure 0.5MPa, the charging mass space velocity is 0.5h
-1, virgin naphtha enters reaction zone by the order of process furnace, first reactor, process furnace, second reactor and carries out aromatization.The main operational condition of catalyst regenerator is: revivifier pressure 0.7MPa, and one section scorch region resurgent gases temperature in is 470 ℃, oxygen level is 0.5 volume % in the resurgent gases; Two sections scorch region resurgent gases temperature ins are 480 ℃, oxygen level is 0.6 volume % in the resurgent gases, resurgent gases and reclaimable catalyst volume ratio are 3000:1, the residence time of reclaimable catalyst in the revivifier scorch region is 120 minutes, the temperature of drying zone inlet gas is 490 ℃, and the temperature of cooling zone exit gas is 165 ℃.The variation of the maximum carbon-burning capacity of revivifier and the rear catalyst specific surface area of repeatedly regenerating has also been investigated in test.Test-results sees Table 2.
Example 3
By technical process shown in Figure 2, use catalyst A, be that raw material carries out aromatization with the virgin naphtha shown in the table 1, be reflected under the conditions of non-hydrogen to carry out.The operational condition of reactive moieties and revivifier and reclaimable catalyst at the residence time, drying zone gas inlet temperature and the cooling zone gas outlet temperature of scorch region all with example 2, different is that resurgent gases enters two sections scorch regions respectively from the middle part, and test-results sees Table 2.
Comparative Examples 1
Using catalyst A, is raw material with the virgin naphtha shown in the table 1, carries out the non-hydrogen aromatization reaction.The mode of connection of reactive moieties reactor and reaction conditions are all with example 2, and different is that regeneration section adopts prior art, i.e. pressure conversion and flow control district are positioned at the revivifier bottom; Revivifier is made up of scorch region and drying zone two portions, and wherein scorch region is one section radial bed, burns the flue gas drying of generation, and with additional air mixed after return the revivifier scorch region.The main operational condition of revivifier is: revivifier pressure 0.35MPa, oxygen level is 0.75 volume % in the resurgent gases, the resurgent gases temperature in that enters scorch region is 480 ℃, and resurgent gases and reclaimable catalyst volume ratio are 3000:1, and the residence time of reclaimable catalyst in scorch region is 120 minutes.The variation of the maximum carbon-burning capacity of revivifier and the rear catalyst specific surface area of repeatedly regenerating has also been investigated in test.Test-results sees Table 2.
Example 4
By technical process shown in Figure 3, use catalyst A, be raw material with the virgin naphtha shown in the table 1, carry out the non-hydrogen aromatization reaction, each reactor inlet temperature of reaction zone is 400 ℃, reaction pressure 0.5MPa, charging mass space velocity are 0.5h
-1, virgin naphtha enters reaction zone by the order of process furnace, first reactor, process furnace, second reactor, process furnace, the 3rd reactor, process furnace, the 4th reactor.The main operational condition of revivifier is: revivifier pressure 0.7MPa, and one section scorch region resurgent gases temperature in is 470 ℃, oxygen level is 0.5 volume % in the resurgent gases; Two sections scorch region resurgent gases temperature ins are 480 ℃, and oxygen level is 0.6 volume % in the resurgent gases.The volume ratio of resurgent gases and reclaimable catalyst is 3000:1, and the residence time of reclaimable catalyst in the revivifier scorch region is 120 minutes, and the temperature of drying zone inlet gas is 486 ℃, and the temperature of cooling zone exit gas is 160 ℃.The variation of the maximum carbon-burning capacity of revivifier and the rear catalyst specific surface area of repeatedly regenerating has also been investigated in test.Test-results sees Table 3.
Example 5
By technical process shown in Figure 4, use catalyst A, with the virgin naphtha shown in the table 1 is raw material, carry out the non-hydrogen aromatization reaction, all with example 4, different is that resurgent gases enters two sections scorch regions respectively from the middle part at the residence time, drying zone gas inlet temperature and the cooling zone gas outlet temperature of scorch region for reaction zone operational condition, virgin naphtha charging order, revivifier operational condition and reclaimable catalyst.Test-results sees Table 3.
Comparative Examples 2
Using catalyst A, is that raw material carries out the non-hydrogen aromatization reaction with the virgin naphtha shown in the table 1.The mode of connection of reactive moieties reactor and reaction conditions are all with example 4, and different is that regeneration section adopts prior art, i.e. pressure conversion and flow control district are positioned at the revivifier bottom; Revivifier is made up of scorch region and drying zone two portions, and wherein scorch region is one section radial bed, burns the flue gas drying of generation, and returns the revivifier scorch region after the additional air mixed.The main operational condition of revivifier is: revivifier pressure 0.35MPa, oxygen level is 0.75 volume % in the resurgent gases, the resurgent gases temperature in that enters scorch region is 480 ℃, and resurgent gases and reclaimable catalyst volume ratio are 3000:1, and the residence time of reclaimable catalyst in scorch region is 120 minutes.The variation of the maximum carbon-burning capacity of revivifier and the rear catalyst specific surface area of repeatedly regenerating has also been investigated in test.Test-results sees Table 3.
By the data of table 2, table 3 as can be known, the inventive method has higher liquid yield and aromatics yield than Comparative Examples, product liquid octane value height, and xylene content wherein is also higher.In addition, the high carbon content of the reclaimable catalyst that the inventive method allows is big, and catalyzer loses little through regeneration back specific surface area repeatedly, thereby can be arranged higher work-ing life.
Table 1
| Boiling range, ℃ | 36～158 |
| Alkane, quality % | 58.6 |
| Naphthenic hydrocarbon, quality % | 36.5 |
| Aromatic hydrocarbons, quality % | 4.9 |
| Basic n content, μ g/g | 1.4 |
| S content, μ g/g | 157 |
Table 2
Table 3
Claims (21)
1. a continuous aromatization modification method for hydrocarbons comprises the steps:
(1) hydrocarbon raw material heating back is sent into from the top in the moving-burden bed reactor to contact with aromatized catalyst and reacted, reaction product obtains gasoline component and liquefied gas through fractionation,
(2) reclaimable catalyst that is come out in the moving-burden bed reactor bottom, being promoted to reclaimable catalyst separation hopper by the reclaimable catalyst lifter through lift line separates with lifting gas, then through excess pressure conversion and flow control district, enter catalyst regenerator from the top, pass through buffer zone, scorch region, drying zone and cooling zone in the catalyst regenerator from top to bottom successively, in scorch region, feed the coke burning regeneration that oxygen containing resurgent gases is carried out reclaimable catalyst
(3) from the effusive regenerated catalyst in catalyst regenerator bottom, separate hopper through regenerated catalyst lifter, regenerated catalyst lift line, regenerated catalyst and enter moving-burden bed reactor.
2. in accordance with the method for claim 1, it is characterized in that described scorch region comprises at least two sections scorch regions of arranged vertical from top to bottom.
3. in accordance with the method for claim 2, it is characterized in that described scorch region is made up of two sections scorch regions of arranged vertical from top to bottom, first scorch region that comes top is a radial bed, and second scorch region that comes the bottom is axial bed.
4. in accordance with the method for claim 2, it is characterized in that described scorch region is made up of two sections scorch regions of arranged vertical from top to bottom, and two sections scorch regions are radial bed.
5. according to claim 3 or 4 described methods, it is characterized in that being mixed into resurgent gases from the flue gas process desulfurization of scorch region discharge and the gas mixture of dry back and air or air and nitrogen, described resurgent gases is divided into two strands, respectively through entering one section scorch region and two sections scorch regions after the heating.
6. in accordance with the method for claim 5, it is characterized in that in two bursts of resurgent gaseses one enters the reclaimable catalyst bed from the top of one section scorch region in entad mode, another strand enters the reclaimable catalyst bed from the bottom of two sections scorch regions in the centrifugal mode.
7. in accordance with the method for claim 5, it is characterized in that two bursts of resurgent gaseses enter one section scorch region and two sections scorch regions respectively from the middle part.
8. according to claim 3 or 4 described methods, it is characterized in that the flue gas of two sections scorch regions generations is discharged from the bottom or the top of one section scorch region.
9. in accordance with the method for claim 5, it is characterized in that the oxygen level of one section scorch region inlet resurgent gases is 0.1～3.0 volume %, the oxygen level of two sections scorch region inlet resurgent gaseses is 0.2～5.0 volume %.
10. in accordance with the method for claim 5, the temperature in that it is characterized in that one section scorch region resurgent gases is 350～600 ℃, and the temperature in of two sections scorch region resurgent gaseses is 400～600 ℃.
11. in accordance with the method for claim 5, it is characterized in that reclaimable catalyst is 10～600 minutes in the residence time of scorch region, revivifier pressure is 0.1～2.0MPa.
12. in accordance with the method for claim 1, it is characterized in that earlier cold gas being fed the cooling zone of catalyst regenerator, the gas that is come out by the cooling zone mixes with dry gas again, enter drying zone after heating, described cold gas and dry gas are selected from the miscellany of nitrogen, air or nitrogen and air.
13. in accordance with the method for claim 1, it is characterized in that the temperature of drying zone inlet gas is 120～600 ℃, the oxygen level in the dry gas is not more than 21 volume %.
Be not more than 200 ℃ 14. it is characterized in that in accordance with the method for claim 1, the temperature of cooling zone exit gas.
15. in accordance with the method for claim 1, it is characterized in that the drying zone expellant gas is discharged system or introduced the scorch region recycle.
16. in accordance with the method for claim 1, it is characterized in that described moving-burden bed reactor comprises the reactor of two to four polyphones, the reaction raw materials that enters each reactor all needs to heat by process furnace.
17. in accordance with the method for claim 1, it is characterized in that described hydrocarbon raw material is that initial boiling point is 30～80 ℃, final boiling point is 130～200 ℃ a hydrocarbon fraction.
18. in accordance with the method for claim 17, it is characterized in that hydrocarbon fraction is selected from the naphtha fraction that virgin naphtha, reformation tops, condensate oil or hydrogenation coking process produce.
19. in accordance with the method for claim 1, it is characterized in that described temperature of reaction of (1) step is 250～600 ℃, pressure is 0.1～2.0MPa.
20. in accordance with the method for claim 1, it is characterized in that described aromatized catalyst active ingredient is high silicon pentasil zeolites or contains zinc or the high silicon pentasil zeolites of gallium, rare earth and VA family element.
21. in accordance with the method for claim 20, it is characterized in that described high silicon pentasil zeolites is selected from ZSM-5, ZSM-11 or ZSM-12 zeolite, described rare earth is a mishmetal, and VA family element is phosphorus, antimony or bismuth.
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| US8604262B2 (en) * | 2011-04-29 | 2013-12-10 | Uop Llc | Process for increasing aromatics production |
| CN103789015B (en) * | 2012-11-02 | 2016-05-11 | 中国石油化工集团公司 | The round-robin method of a kind of counter-flow moving bed continuous reformer and catalyst |
| US8900442B2 (en) * | 2012-11-20 | 2014-12-02 | Uop Llc | High temperature CCR process with integrated reactor bypasses |
| US8906223B2 (en) * | 2012-11-20 | 2014-12-09 | Uop Llc | High temperature reforming process for integration into existing units |
| CN104140847B (en) * | 2013-05-10 | 2015-12-23 | 中石化洛阳工程有限公司 | A kind of F-T synthesis petroleum naphtha upgrading produces the method for stop bracket gasoline |
| CN104289257A (en) * | 2013-07-19 | 2015-01-21 | 中国石油天然气股份有限公司 | Regenerator for reducing dead zone catalyst |
| CN114478180B (en) * | 2020-10-27 | 2024-05-17 | 中国石油化工股份有限公司 | Method for lightening heavy aromatic hydrocarbon |
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| CN1063121A (en) * | 1992-03-05 | 1992-07-29 | 中国石油化工总公司洛阳石油化工工程公司 | Catalytic modification of poor quality gasoline-aromatization |
| US5164071A (en) * | 1989-04-17 | 1992-11-17 | Mobil Oil Corporation | Fluidized catalyst process for upgrading olefins |
| CN1080313A (en) * | 1992-03-05 | 1994-01-05 | 中国石化洛阳石油化工工程公司 | Catalytic upgrading-aromatization process of poor gasoline |
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| US5164071A (en) * | 1989-04-17 | 1992-11-17 | Mobil Oil Corporation | Fluidized catalyst process for upgrading olefins |
| CN1063121A (en) * | 1992-03-05 | 1992-07-29 | 中国石油化工总公司洛阳石油化工工程公司 | Catalytic modification of poor quality gasoline-aromatization |
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